Fuel oil compositions



This application is a continuation-in-part of our copending application Serial No. 532,121, filed September 1, 1955, and Serial Nos. 548,748 and 548,749, filed November 23, 1955.

The present invention is concerned with a fuel composition Which has been stabilized by means of an additive against the formation of sludge and undesirable color bodies, especially under high temperature conditions as in diesel and jet fuel engines where the fuel is preheated for some time before consumption and thereby introduces in additional problem of thermal instability. The deterioration of hydrocarbon fuel oils, and more particularly furnace oils, diesel fuels, jet engine fuels, distillate fuel oils, so-called middle oil distillates, and the like is a commonly recognized problem.

The problem, particularly from the standpoint of sludge formation in domestic heating oils and diesel oils, is set forth in US. Patent 2,793,943, dated May 28, 1957, to Moore. As to discoloration, reference is made to U.S. Patent 2,711,947, dated June 28, 1955, to Smith et al.

The distillate hydrocarbon fuels useful in forming the compositions of the invention can have a boiling range of 135 F. to 700 F. Conventional jet fuels, since they are blends of gasoline and kerosene fractions, normally have a Wide boiling range with an initial boiling point of as low as about 135 F., and an end point as high as 600 F. Conventional diesel fuels also normally have a rather wide boiling range of about 350 F. to 700 F. or higher. The amount of inhibitor in the compositions of the invention is generally in the range of about to 500 parts per million. This is equivalent to about 0.2 to about 10.4 milliliters of inhibitor to each 5.5 gallons of distillate hydrocarbon.

The fuels of this invention are particularly useful in engines, such as jet and diesel engines, where the fuel is subjected to elevated temperatures prior to combustion and the problem of thermal stability of the fuel arises.

Fuels which are not thermally stable, when employed in, forexample, jet and diesel engines, tend to decompose With the formation of sludge, gums and other carbonaceous materials in the fuel system components which are maintained at an elevated temperature. These decomposition or degradation products then deposit on the walls or in small passages of the fuel system, such as the injection nozzles, causing their malfunction.

It has now been found that distillate hydrocarbon fuels which tend to form sludge and/or discolor and/or are not thermally stable can be improved with respect to these characteristics by the incorporation therein of a small amount of the reaction product obtained by reacting at a temperature of about 100 to 300 C. for from about 1 to 4 hours (A) an oxirane ring containing compound selected from the class consisting of epoxidized fatty acids, epoxidized higher fatty acid esters, epoXidized higher fatty acid amides, epoxidized higher fatty alcohols and epoxidized higher fatty acid glycerides, with (B) an oxyalkylation-susceptible nitrogen containing compound selected from the class consisting of hydrazine and monoamino and polyamino compounds composed of carbon, hydrogen, oxygen and nitrogen atoms, having only functional groups selected from the class consisting of hydroxyl groups, primary amino groups and secondary amino groups and having at least tes Patent one such functional amino group; said reaction between (A) and (B) involving rupture of the oxirane ring and For purpose of convenience, what is said hereinafter .Will be divided into four parts;

Part 1 is concerned with the derivatives obtained by the epoxidation of fatty acids or the like, and generally characterized by the presence of at least one oxirane ring per fatty acid molecule:

Part 2 is subdivided into eleven sections, and is concerned with amino compounds which are non-resinoid in nature and may or may not include in their structure a hydrophobe group, i.e., a group having 8 or more uninterrupted carbon atoms in a single radical, or the like. Such amino reactants must contain a reactive hydrogen atom generally attached to either nitrogen or oxygen. The presence of such reactive hydrogen atom is necessary for reaction with the oxirane ring. Stated another way, such reactants must be oXyalkylation-susceptible.

Part 3 is concerned with reactions involving the two classes of reactants above, i.e., those described in Part 1 and those described in Part 2;

Part 4 is concerned with the reaction products of Part 3.

PART 1 The epoxidation of ethylenic compounds and particularly esters of unsaturated fatty acids amides of unsaturated fatty acids, naturally occurring glycerides, unsaturated aliphatic alcohols, and the unsaturated fatty acids themselves, is well known. For instance, it has been described in the following patents:

US. Patents Nos.

amines. The monoamines are primary or secondary amines which can or need not contain one or a plurality of hydroxyl radicals. The monoamine, if primary, can be treated with an alkylene oxide to yield a hydroxylated secondary amine.

In addition to the monoand di-methyl, ethyl and propyl amines, other monoamines include the following:

n-Butyl amine Furfurylamine Dibutyl amine Dodecylamine 2-ethylhexyl amine Monoethanolamine Di(2-ethylhexyl) amine Diethanolarnine Monoisopropanolamine N-methyl ethanolamine Diisopropanolamine N-ethyl ethanolamine Methyl isopropanolamine Butyl isopropanolamine Hexylamine n-Amylamine Di-n-amylamine Sec-amylamine Patented Aug. 15, 1961 distillate fuels containing Dihexylamine N-ethylbutylamine Heptylamine 2-amino-4-methylpentane Octylamine 4-amino-2-butanol Dioctylamine S-isopropylamino-l-pentanol Decylamine N-butylaniline Similarly, secondary high molecular weight aliphatic amines known as Armeen 2C and Armeen 2HY can be used.

Also, high molecular weight aliphatic amines known as Armeen 10, Armeen 16D, Armeen HTD, Armecn 18D, and Armeen CD can be used.

Suitable amines having an aromatic ring include alphamethylbenzylamine and alpha-methylbenzylmonoethanolamine.

Other amines include:

Z-amino-Z-methyl-l-propanol 2-amino-2-methyl-1,3-propanediol 2-amino-2-ethyl-1,3-propanediol 3-amino-2-methyl-l-propanol 2-amino-1-butanol 3-amino-2,2-dimethyl-l-propanol 2-amino-2,3-dirnethyl-l-propanol 2,2-diethyl-2-amino ethanol 2,2-dimethyl-2-aminoethanol 3-amino-l,2-butanedio1 4amino-l,2-butanedio1 2-amino-1,3-butanediol 4-amino-l,3-butanediol 2-amino-l,4-butanediol 3-amino-1,4-butanedio1 1-amin0-2,3-butanediol Tris-(hydroxy methyl) amino methane Amines having ring structures of course include aniline, diphenylamine, cyclohexylamine, dicyclohexyb amine, and various comparable amines with alkyl substituents in the ring.

Other suitable amines are those obtained from sugars or comparable derivatives, such as glucamine and maltos Section 2 The polyamines which may be employed as reactants fall within two types. The first type is characterized by the fact that the polyamines have at least one primary amino radical separated from another primary or secondary amino radical by two to three carbon atoms in a single chain. These polyamines under certain conditions can form cyclic amidines and thus are importantfrom what is said in Part 6, subsequently.

One may use polyamines. corresponding to. the formula in which R is hydrogen, alkyl, cycloallcyl, aryl, or. aralkyl and R is a divalent radical such as Stated another way, the polyamines have at least one primary amino group separated from another primary or secondary amino group by 2 to 4 carbon atoms. Examples of suitable amines include:

Ethylenediamine Diethylenetriamine Triethylenetetramine Tetraethylenepentamine Propylenediamine Dipropylenetriamine Tripropylenetetramine Butylenediamine' Aminoethylpropylenediamine Aminoethylbutylenediamine Other polyamines in which the nitrogen atoms are separated by a carbon atom chain having 4 or more carbon atoms include the following: Tetramethylenediamine, pentamethylenediamine, and especially hexamethylenediamine. The latter is of particular interest because the product is commercially available in light of its use in the manufacture of synthetic fibre;

If desired, one can prepare a variety of reactants having two or more amino groups and at least one hydroxyl group. One may use modifications of procedures or the procedures themselves as described in US. Patents Nos; 2,046,720, dated July 7,, 1936, to Bottoms; 2,048,990 dated July 28, 1936, to Britton et al.; 2,447,821 dated August 24, 1949, to Sankus; and 1,985,885 dated January 1, 1935, to Bottoms. Examples includethe following:

CH3 /CH8 N-CHiCH2"-N on. omonononmm CzHs GHQ-CHE f-omom-rr C aCH, CHaCHOHOHaNH:

CH5 CH3 --CHzCHr-N NHaCHlCHOHCH: CHQCHOHOHOHCILNHQ Other suitable amines are exemplified by ethylenebisoxypropylamine,

C1120 CHzCHgCHzNH H2O CH1 CH: C HINH and derivatives obtained by treating ethylenebisoxypropylamine with '1, 2, 3, or 4 moles of ethylene oxide, propylene oxide, butylene oxide, or the like.

Other compounds including those having cyclic structures include piperazine, and the corresponding derivatives obtained by treating piperazine with alkylene oxides. The same applies to substituted piperazine such as the 2,5-dimethylpiperazine.

As to mono-substituted dialkanol piperazine see U.S. Patent No. 2,421,707, dated June 3, 1947, to Malkemus:

Section 3 Mample poiyamine wiaich may be employed as a reactant is the kind described as Duomeens.

TABLE 1 Duomeen is a trademark designation for certain diamines. Dllomeens have the following general formula:

R is an alkyl group derived from a fatty acid or flom the mixed fatty acids as obtained from certain oils. The specific Duorneen and the source of the radical R are as follows: i

(1) Duomeen 12-R=-lauric 2) Duomeen C-R=Coconut oil fatty acid (3) Similarly, a comparable diamine, presumably obtained from Rosin Amine D and acrylonitrile, can be prepared. The structure of Rosin Amine D is as follows:

CH3 OHzNHI Ha CH! Polyamines from monoamines and cyclic imines, such as ethylene imine.

H C1QH21N C tHa-NH: N -deeyl butylenediamine Polyamines containing tertiary amino groups It is to be noted that all the above examples show high molal groups, i.e., 8 carbon atoms or more. The same derivatives in which methyl, ethyl, propyl, butyl, amyl, hexyl groups, or the like, appear instead of octyl, decyl, etc., are equally satisfactory.

Section 4 Polyamines of the kind described above, i.e., those having at least one primary amino radical separated from another primary or secondary amino radical by two to three carbon atoms in a single chain, can be converted into a number of products which in turn still have the characteristic requirements previously noted, i.e., are still oxyalkylation susceptible. A good example is a cyclic amidine obtained from a polyamine. This may be illustrated by the following table:

TABLE 2 a undecylimldazoline N-CH,

2-heptadecyllmidaiollne CnHuC 1-dlethylenediamlne-Z-undecyleneyllmldazoline N- C H:

Tetrahydropyrimidines from monocarboxy acids and trimethylenepolyamines.

(3) N-CH2 CH Ma 1amlnoethylamino'ethyl, 2-dodecyl, 4-methy1 tetrahydropyrimldins Cyclic amidines are derived conveniently fiom carboxy acids, including polycarboxy acids. As is well known, some polycarboxy acids have 3 or more carbonyl radicals; thus, it is possible to obtain cyclic amidines in which 3 or more ring radicals appear. The present invention, however, is limited to cyclic amidines having not over 2 ring radicals and preferably only one ringradical.

suitable as reactants for the present purpose.

Cyclic amidines having more than one ring radical are illustrated by the following formulas:

R=hydrocarbon radical containing 8-32 carbon atoms.

Cyclic amidines containing basic tertiary amino groups:

11) N.GH|

It is to be noted that all the above examples show high molal groups, i.e., 8 carbonratoms or more. The same derivatives in which methyl, ethyl, propyl, butyl, amyl, hexyl groups, or the like, appear instead of groups having 11, l2, 17 or 19 carbon atoms, are equally satisfactory.

Section 5 Actually, cyclic amidines of the kind, described previously are obtained in many instances from amides as intermediates in amidine manufacture. Suitable amides derived from amines of the kind described previously are Such amides are shown in the following table:

TABLE 3 E No.

H H Ci'1 s5-' 2 4NH':"

aminoethylstearamide 2 V H H H CnHsa-C-N-CzHA-N-CgHi-NH,

aminoethylaminoethyloleamlde I] H H CnHnCN-CaHu-NCtHo-NH1 sminopropylaminopropyldeeanoamide 4 o g H H H Cus a1 NC4Hs-NC:H4N--C:H4-NH aminoethylaminoethylaminobutylpalmitamide 5 O g H Cin 2o N.--OH -CH NH aminoethylabietamide II E CwHzrO-N-dlaHs-NH: aminopropylabletamida Diamides may be obtained from polyamines and 2 moles of acid. V

as monocarboxy acids. 7 Thus it is possible to get poly- I as 8 amides by using acids containing more than one carboxyl group, as illustrated in the followingexamples:

Amino amides can be obtained from polyamides in which there is a terminal tertiary amine radical having a basic nitrogen atom. Another procedure involves the production of an amino amide from a polyamine in which the terminal radicals are either primary or secondary .followed by alkylation of the amide so as to convert the residual terminal radical into a basic tertiary amine radical. Another procedure is touse a secondary amine, such as dibutylamine or dihexylamine, and react stepwise with ethylene imine or propylene imine. The polyamine so obtained contains a basic'tertiar'y amino radical. The acylation of such a polyamine results in an amino amide which will form complexes comparable to those obtained from a basic tertiary amine. Examples of such amino amides are as follows:

13 a H H l p ."l CuHar- --N C|HsN-CgH4N-QH| It is to be noted that all the above examples show high molal groups, i.e., 7 carbon atoms or more. The same derivatives in which methyl, ethyl, propyl, amyl, butyl, hexyl groups, or the like, appear instead of groups having 9, 17, 19 carbon atoms or the like, are equally satisfactory. r I Section One type of hybrid compound includes either an imidazoline ring or a tetrahydropyrimidine ring. Since it is more economical to use the imidazolines rather than the tetrahydropyrmidine's this particular type will be illustrated but it is understood that either type can be used. One example is an instance in which the imidazoline radical appears, and also'a high molal radical, for instance, a C13H1q radical. In this instance there are two high molal groups: W I

i /NCB| w s-9%- Hg 7 I ("JQHLNH. CzHcNH. CnHn Actually a cyclic amidine having a hydroxyalkyl group may be esterfied, provided that there is still a reactive hydrogen atom for combination with the epoxidized compound. This is illustrated by the following:

' /N-CH:

esnm r V The type in'which there is an imidazoline ring and only one high molal amino group is illustrated in the following:

If one employs a dicarboxy acid'having 8 ozmore carbon atoms indicated by R(C0OH) then com-pounds of the following type can be prepared: t

-It is obvious that a high molal amine such as N-dodecyl diethylenetn'amine having the formula Similarly, if the dodecyl diethylene triamine is treated with a mole' of ethylene oxide or preferably 2 moles of ethylene oxide so as to have a terminal radical, thus:

' Needless to say, a compound such as dodecyl diethylene triamine previously illustrated can be converted into an imidazoline by conventional procedure, such a procedure already has been described above. The imidazoline may be derived from either a low molal acid, i.e., acetic acid, or a high molal acid, such 0s oleic acid.

Similarly, an amine of the following type:

can be converted into an oxazoline by using either'alow molal monocarboxy acid or a high molal monocarboxy acid; or if the C H radical above is replaced by a CH radical suitable compounds are obtained using a higher fatty acid, such as oleic acid.

Such compounds can be illustrated by the following:

The introduction of a pent-oxazoline group requires the use of a reactant such as the following:

o I 0 7139560 CzHaN-CHz-CHr(-CH2CH2C-CHz -CHzNHz The previous examples seem to be more than ample for purpose of illustration. It is to be notedthat combi- 10 nations in which at least three different types of radicals appear are readily obtainable by reacting an imidazoline obtained from a tetramine or pentamine with an acid, such as acetic acid or oleic acid so as to yield an amido imidazoline and then react such product with a glycidyl ether of the type in which R'reperesents a low or high molal group. Similarly, an imidazoline may be subjected to oxyalkylation and then to esterification followed by the use of glycidyl ether of the kind above described.

Likewise, another type of reactant .is represented by compounds of the following structure which have been described in the patent literature See Journal of the American Chemical Society, volum 68 (1946), page 1291.

Compounds containing the oxazoline ring or pentoxazoline ring and derived from a dicarboxy acid can employ the carboxyl radical so as to combine to form an imidazoline ring as previously described, or obviously to combine with an amine to form an amide group, or with a polyamine to from not onlyan amide group but also a. compound which again can be reacted with an aminoglycidyl ether as above described to introduce a high molal group. Furthermore, such carboxyl group could be esterified with triethanolamine or the like, or with a comparable polyamine to produce an amino ester.

Attention is directed to the'fact that a compound such as N-octadecyl N,N',N' tris-2-hydroxyethyl-1,3-trimethylene diamine having the following formula CHICHQOH OH CH OH CmHsr-N-CHzCHzCHgN CHzCHaOH can be esterified with acetic acid or oleic acid to introduce an amino ester radical. Similarly, the amino ester so derived can be reacted in turn with an alkylene imine such as ethylene imine or propylene imine and then reacted with another mole of acid so as to introduce a third type, to wit, an amido type radical.

Section 7 An interesting group of compounds which have been noted previously are the non-cyclic amidines having the general formiila where R and R are either orboth an alkyl group or hydrogen, and n, an integer from 7-to 1 3. See British Patent 518,575. p

Specific examples described in said British patent include the following: 0 NH (C2Hs. s.N.(C 2)1o.C

kappa-diethylamino-n-undecane amidlne kappwdlbutylamlno-n-undecane amldlne mazes NH 7. 4 10) 2- 2)u,

lambda-dibutylamlno-n-dodecane a-mldtne NH fl s) 2.N.( 2) 11-0 NH: lambda-diethylamlno-n-dodecane amldine NH NHz.(OH 1)10. O

kappa-amlno-n-undecane amidlne Other suitable polyarnino compounds may contain acyl radicals or an acyl radical residue from low molal monocarboxy acids as, for example, acetic acid, propionic acid, butyric acid, hydroxyacetic acid, lactic acid, etc. This applies not only to cyclic amidines but also other compounds such as high molal polyamines, esters of hydroxylated polyamines, etc. Purely by way of example attention is directed to the following formulas which illustrate such compounds:

N-w H:

zHLN. CIHLNHOCLCHI Needless to say, the same comparable compounds can be obtained from another type of cyclic amidine, to wit, a tetrahydropyrimidine.

Other examples suitable for the present purpose are obtained by reacting high molal diamines of the formula.

H H N HE 1 2 whereR varies from 8 to 18 and particularly from 12- to 18, with a single mole of low molal monocarboxy acid such as acetic acid, propionic acid, butyric acid, etc.

Section 8 In many instances monoamines can be reacted with ethylene imine, propylene imine, or a dialkyl amino 'e poxypropane such as wherein R and R" are alkyl groups, to convert a monoamino compound into a polyamino compound. This can be illustrated by suitable polyarnino compounds having an oxazoline ring (S-membered or 6-mernbered).

TABLE 5 General Reaction:

Q3: H 5 I +1100 on E EsQ -QHn H Hr Y QE I-ZEQQ E NH: H N

2 amJno-Z-methyl-l,3-propanedtol EeeaIJsfl Stearic Acid CH (CH 5COQH $H: HOCHr-(|3'-([JH:

\C JEM HMAAE; (A)

Ole c Acid AH OH:CH(C.H2)1 OH CH: HOC,H:-+-CH:

C ctflucnwawmnom (B) Laurie A id CH3(CH2)16CQQH CEI 'HocH men,

4 CHa(CHI)9( 3'H: (G)

Let R OH be the simplified structure for all the four hydroxyethyl oxazolines. General Reaction:

13 (1) A)+ethylene imine CHa H2N-CH:-CH20GHa-? CH2 OHa(CH2)1s H2 (2) (B)j+ethylene imine HgN-CHg-CHsO-CHr- I -CHZ N\ \C CaHnCHzCHWHflNEH;

3; (CH-ethylene imine HzNCHg-CHrCHgO-CHz- I -cH,

c CHKCHQMBH: (4) (A) +propylene imine General Reaction:

is (G) +Rcoorr where nrc rr iR=CnHgs n ai Section 9 amines such as the polyethylene amines previously described, i.e., triethylene tetramine, tetraethylene pentamine, etc., and certain alpha-beta unsaturated acids such as acrylic acid, crotonic acid, methacrylic acid, agelic acid, and sorbic acid.

It will be noted one can also prepare such products from nondistillable polyethylene amines, for instance, the residual mixture in polyethylene manufacture which consists largely of pentaethylene hexamine or hexaethylene heptamine. Using such high amino compounds having, for instance, 6 or 7 nitrogen atoms per molecule one can obtain reactants which have as many as 20 nitrogen atoms in the molecule. Similarly, one can react dicarboxy or tricarboxy acids with 2 or 3 moles of the same polyamines having 5, 6 or 7 nitrogen atoms and obtain amides, polyamides or combinations in which cyclic amidine groups also appear and which may like wise have as many as 10 to 20 nitrogen atoms per molecule. In a general way, compounds of the types just referred to having up to 20 nitrogen atoms per molecule represent a practical upper limit in many cases.

Section 10 Said aforementioned co-pending Shen application, Serial No. 521,387, filed July 11, 1955, also describes another class of material which can be used as reactants in the present invention, to wit, a somewhat analogous class of disubstituted cyclic amidines has been illustrated in which one substituent does not necessarily have a nitrogen atom. This is an instance of the kind in which hydroxyethyl ethylene diamine, hydroxypropyl ethylene diamine, hydroxybutyl ethylene diamine, hydroxyethyl 1,3- propylene diamine, hydroxylpropyl 1,3-propylene diamine, hydroxybutyl 1,3-propylene diamine, or the like, is used to give a type of compound previously illustrated to wit,

CHI -CH;

JJHgCHaNHCHzCHgNHCHgCHgOH Furthermore, the precursory diamines of the kind referred to above can be reacted with other alkylene oxides such as glycide, methyl glycide, allyl glycidyl ether, glycidyl isopropyl ether, glycidyl phenyl ether, styrene oxide, etc., on a mole-for-mole basis. The resultant of such reaction can be used in the same manner as the substituted diamines above noted.

The type of compounds described in aforementioned Shen application, Serial No. 521,387, filed July 11, 1955, are particularly valuable as reactants for the reason that either the class of materials described in Section 8, preceding, or in the present section, can be prepared free from any high molal group or a group which has at least 8 uninterrupted carbon atoms. Therefore, particularly valuable products are obtained by combination with the epoxidized products herein described which in turn supply a high molal group.

Attention is again directed tothe fact that the polynitrogenous reactants preferably contain at least one basic nitrogen and preferably two or more. Furthermore, it is preferable that there be present at least one, and preferably two, primary amino groups. If one reacts ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, or the like with 2 moles of a low molal acid such as acetic acid, propionic acid, butyric acid, or with a higher fatty acid such as oleic acid or stearic acid, or a combination of the two, one can obtain a compound having 2 arnido radicals in which there is no basic nitrogen atom. If one uses one mole of an acid there is a single basic nitrogen atom. Our preference, however, is to use compounds in which there are at least 2 basic nitrogen atoms and preferably having at least 2 basic primary amino groups. For this reason the preference in many instances is to employ polyamines such as diethylene triamine, triethylene tetramine, tetraethylene pentarnine, etc. In a large number of the examples which have appeared in the sections preceding, the compounds illustrated have high molal radicals, for instance, one having 8 to 18 carbon atoms. It is again desirableto point out that this is no limitation to the broad aspect of the invention. In each instance such high molal radicals can be replaced by a methyl group, ethyl group, propyl group, butyl group, amyl group, hexyl group, heptyl group, or the like.

Phenylenediamine represents an example ,of a polyaimine which contributes substantially no basicity to the product of reaction.

Section I] V Another type of compound which may be reacted with the epoxidized derivatives are the 'hydrazines andhydrazine derivatives of the kind which have been described in numerous patents. Although hydrazine, particularly the hydrate, can be reacted with epoxy compounds provided, of course, that extreme caution is taken to avoid any hazard, we have found it of equal interest to use beta hydroxyethyl hydrazine which is commercially available.

Other compounds which may be employed are those which correspond to the formula ,The acyl radical RCO can be derived from a low molal acid or a high molal acid such as stearic acid.

See also U. S. Patent No. 2,371,133 which describes hydrazine derivatives containing hydroxyalkyl radicals formed by condensing one molof a hydrazide of an aliphatic carboxylic acid containing at' least 2 carbon atoms, which hydrazide contains at least one hydrogen atom bound to ahydrazine nitrogen atom, with at least one mol of an alkylating agent which is capable of introducing an aliphatic radical containing the grouping --CC and also hydroxyl groups.

As to the manufacture of Z-hydroxyethyl hydrazine see U. S. Patent No. 2,660,607 dated November 24, 1953, to Gever et al.

Note also that low polymers of hydrazine or similar compounds, such as polymethylenedihydrazines of the formula H N.NH.(CH .NH.NH may be employed as a reactant with the epoxidized derivatives.. For further description of such polymethylene dihydrazines see U. S. Patent No. 2,445,518 dated July 20, 1948 to Dreyfus.

PART 3 Part 3 is concerned with reactions between the two classes of reactants described in the foregoing, i.e.,'those described in Parts 1 and 2.

16 For purpose of brevity we are going to limit the examples to products which are available commercially or can be obtained from suppliers of epoxidized products. These products are the following:

(1) Epoxidized soy bean oil (2) Epoxy butyl stearate (3) Isobutylepoxyacetoxy stearate (4) Methylepoxy soyate (5 Epoxidized triacetylated castor oil (6) Epoxidized alcohol derived from soy bean fatty acid.

As previously pointed out the reaction involving the reactant containing the oxirane ring and the selected compound having a labile hydrogen atom is essentiallya variety of oxyalkylation. For this reason the reactions are so conducted. The procedure is simpler than is the case when ethylene oxide or propylene oxide is used for the reason that the reactants are non-volatile as a rule and thus one does not have to use an autoclave or similar equipment. Furthermore, many of the reactants employed are basic in character and thus to the extent required act as their own catalyst. As has been pointed out elsewhere catalysts can be added, particularly alkaline catalysts such as sodium methylate, caustic soda, caustic potash, etc. In a general way, the procedure employed in preparing the reactants is the same and the only precaution taken as a rule is to avoid temperatures above that required to rupture the oxirane ring for the reason that side reactions or secondary reactions may take place. The procedure is illustrated by examples 1a and 13a and then by Tables 6 through 12, which present the data covering the preparation of a wide variety of products from the reactants described previously.

Example 1a A 300 ml. three-necked flask was fitted with a reflux condenser, a thermometer, and an efficient sealed stirrer. In the flask was placed 150 grams of Admex 711 (epoxidized soybean oil) and 43 grams of diethylene triamine. The mixture was first stirred for 10 minutes to insure thorough mixing; then heat was gradually applied to bring its temperature to C, within half an hour. The reaction was allowed to continue. atlOS C. for 3 hours. Then the temperature was raised to 130 C. to complete the reaction. The product was an amber colored viscous liquid, soluble in xylene and isopropyl alcohol and emulsifiable with water.

Example 13a In the same equipment as used in Example 1a, 175 grams of the epoxybutyl stearate were used along with 49 grams of diethylene triamine. No added catalyst was employed. The reaction took place readily at C., the time required was 3 hours. The final product was a brown liquid, soluble in both xylene and isopropanol and having definite surface active properties.

Additional examples appear in the following tables.

TABLE 6 arys Ex; Oxirane ring containing Amt, oxyalkylation susceptible Arniz, sodium Temp., Time, Product of reaction No. reactant gms. reactant gms. meghyl- 0. hrs.

. a e, gms. "1a---" Epoxidlzed soybean 011.. 15o Diethylene triamine 57 10s 3 Amber viscous liq. sol. in xylene and l t 130 0.5 isopropan 2a.--. do Amine 333 57.6 105 3 Orange viscous liq; sol. in xylene and 0. 5 isopropauol. 3a do Hydroxyethyl ethylene di- 55.4 105 3 Yel. vise. liq. sol. in xylene and V am me. 130 0.5 isopropanol. 7

to do 125 Cyclohexylamine -46 120 2 Brn. vise. liq. sol. in xyl. and 150- 2 propanol. 5a do 125 Mnrnbnlina 40.3 120 3 Yel. visc.11lq. sol. in xyl. and'lsopropane 6a-. do 125 Furtury i .45 130 3 Dk. brn. liq. soluble in xylene and I isopropanol. g

TABLE 7 ae- Ex. Oxirane ring containing Amt, Oxyalkylation susceptible Amt, sodium Temp., Time, Product of reaction No. reactant gms. reactant gms. meghyl- 0. hrs.

a e m.

Epoxybutyl stearate 60 Dimeric acid diimidazoline---- 178 125 3 Black semi-solid sol. in xylene. do 184 Anncen 18 157 110 g Brn. visc. liq. sol. in ale. and xylene.

150 5 184 Aminoethyl stearamide 155 110 g 5 Dk.1brn. visc. liq. sol. in alcohol and 5O Xy 184 Bisimidazoline from digly- 68 1. 7 120 2 Elk. viscous liq. sol. in ale. and Xylene.

colic acid. 160 2 150 Hydrazine 13. 7 110 3 White creamy emul. with 5% H in hydrazine sol. in hot xyl. and isopropanol. Crystalline in cold xyl. and isopropanol. 175 Ethylene diamine 110 3 Brn. liq. sol. in xyl. and isopropanol. 175 Diethylene triamine. 110 3 Do. 150 Triethylene tetramine. 110 3 Do. 175 Tetraethylene pentamine 110 3 Blntliq. sol. 1n xyl. isopropanol and we er. 150 Propylene diamine 110 3 o. 150 Propylene triamine 110 3 Brn. liq. sol. in xyl. and isopropanol. 150 Dnomeen S 130 3 Lt. brn. semi-sol. solu. in xyl. and

isopropanol. 150 Hydroxyethyl ethylene di- 115 3 Lt. brn. 1iq., sol. in xyl. and isoamine. propanol. 150 Aminobutanol 125 3 Dk. brn. liq. $01. in xyl. and isopropanol. 150 Aminoethyl propanediol 125 3 Red vis.-1iq. sol. in xyl. and isopropanol.

TABLE 8 (Fatayst Ex. Oxirane ring containing Amt., Oxyalkylationsusoeptible Amt, sodium Temp., Time, Product of reaction No. reactant gms. reactant gms. metthyl- 0. hrs.

a e gms.

22a. Isomtyjlepoxy acetoxy 241 Diethanol amine 42. 8 1. 4 130 3 Lt. hrn. liq. sol. in xylene and alcohol.

s eara e. 23a do 241 Trishydroxymethylamino- 57.5 1.5 115 3 Brn. liq. sol. in xyl. and alcohol.

ethane. 170 2 24a. ,-do 241 1,6 hexa i i 60. 5 115 3 Do. 25a do 241 Oyclohexylamine 40.5 130 3 Dk. lorn. liq. sol. in xyl. and alcohol. 26w--- do 241 Diphenylamine" 69.0 158 3 Do.

1 27a. do 241 m-Phenylene diamine 44. 0 5 Black vise. liq. sol. in xyl. and alcohol.

TABLE 9 9? Ex. Oxirane ring containing Amt, Oxyalkylation susceptible Amt, sodium Temp., Time, Product of reaction N o. reactant gins. reactant gms. mleihy- 0. hrs.

a e m.

2811.--. Methyl epoxysoyate 150 Ethylene diamine (78%)-... 38 120 g Brn. vis. lliq. sol. in xylene and iso- .5 propano 29a ..do 150 Propylene diamin 37 120 1.5 Drk.})r1n. vie. liq. sol. in xyl. and

50 0.5 co 0. 300.-- do L. 150 m-Phenylene diamine 54 1&0 g Dllll. very vis. liq. sol. inxyl. and

5 a oo o 310...- do 1 160 Hydrazine 17 110 3 White creamy liq. sol. in hot xyl. and

isopropanol. 3211.--- 150 Diethanolamine 53 1 130 3 Brn. vis. liq. sol. in xyl. and alc. 3311...- Rosin Amine D $0 3 Lt. yel. liq. sol. in xyl. and alcohol.

. 5 0. 5 34a- 150 Morpholine 45 3 Yel. vis. liq. sol. in xyl. and alcohol. 3511---- 150 Hydroxyethyl ethylene di- 53 105 3 Yel. vis. liq. xyl. and isopropanol amine. 0. 5 soluble. 36a Furiuryl amine 49 130 3 Drkl. brn. vis. liq. xyl. and isopropanol 1 Methyl epoxysoyate-Epoxidized methyl ester or soyabean fatty acid.

Oxyethylated Rosin In Tables 6 to 12, reference has been made to products by their trade name or equivalent, all of which'areklescribed in detail in the text immediately following:

proportions.

- hydroabietylamine.

linoleic acid.

Amine D is atechnical g'rail'oi de- -derived from-soya fatty acid.

"oyabean oil.

Armeen' 18 is a technical grade of stearylamine. Duomeen' S'is an amino propyl' alkylamine,

'riimln io ys Ex. Oxirane ring containing Amt., Oxyalkylation susceptible Amt, So dlu n1 Temp., 'lirne, Product of reaction No. reactant gms. reactant gms. methy- O. hrs.

late, gms.

37a. Epoxidized triacetylated 162 Propylene triamlne 27. 6 110 3 Drk brn. semi-sol. 50111. in xyl. and

caster o' isopropanol. 38a- 162 -Aminobutanol.- 27 r 125 3 Brn. vise. liqsol. in xylene and alcohol. 39a.- 162 Aminoethyl propanediol 35. 7 125 3 Drlir. fieil vis. liq. sol. in x l. and

a co 4011-.-- 162 m-Phenylene diamlne ,32. 4 120 2 Elk. vis. semi-s01. 50111. in xyl. and

160 2 alcohol. 41a 135 Aminoethyl stearamide.-. 78 110 3 Brn. vise.1 liq. sol. in xyl. and isopropano r 420.- 189 Hydrazine 12 110 3 White creamy semi-sol. solu. in hot xyl. and hot isopropanol. 43a 135 Stearylamine 89 g Brn. vis. liq. sol. in xyl. and alc. 44a 135 Duomeen S --l00 130 3 -Lt. brn. semi-sol. solu. in xyl. and

isopropanol.

4511...- 135 Rosin amine D; a -79 2 Lt. brn. vise. liq. xyl. in xyl. and alc. 46m--- 108 Dimeric acid dimidazoline 130 3 'Black semi-solid sol. in xylene. I 4711--.- 135 Aminoethyl oleylimidazoline. 130 3 Drllr. lllarii. semi-sol. sol in xyl. and

a c0 0 4811...- 162 N-phenyl-2-methyl*1,2-pro- 49 130 3 Brn. vise. liq. Sol. in Xylene and pane diamine. alcohol.

TABLE 11 9 Y 1 Ex. Oxirane ring containing Amt, Oxyalkylation susceptible Amt. sodium Temp., Time, Product of reaction No. reactant gms. reactant gmS. methy- 0. hrs.

late, gms.

49m.-- Epoxidized alcoholfrom 155 Ethylene d fl 120 1. 5 Vise. brn. liq. sol. in xyl. and alcohol.

soybean oil (epoxi- 150 0.25 dized Unadol 40) 50a. do 155 Tetramethylene pentamine.. 1%?) g Vis. liq. sol. in xyl. and alcohol. 51a. do 155 Amine 333 73 (1): g Lt. brn. vis. liq. sol. in xyl. and alcohol. 5211-.-- 155 Hydroxyethyl etl1ylene dl- .52 1: 5 Lt. brn. liq. sol. in xylene and alcohol.

amine. 150 0.25 5311.--- 155 Diethan0lamine 53 1 3 Brn. vise. liq. sol. in xyl. and ale. 5411...- 155 Rosin amine D" 158 120 2 Lt. brn. vise. liq. Sol. in Xyl. and

150 1 alcohol.

TAB LE' 12 Additive Oxirane containing reactant Amt., Oxyalkylation susceptible reactant Amt., Temp., Time, No. gms. gms. 0. hrs.

Epoxidized soybean oil 150 Ethylene diamirle 45 110(5) 2 5 0 -0. d 100 Triethylene tetmmine 57. 3 125 3 do .125 .Amine 333 67.6 125-130 3 do 150 Amine N0. 1 67. 5 215 2 do 150 Amine 60 230 2. 5 -do 150 Diethylene in 60. 5 125 3 poxybutyl stearate 150 Polyamine 333 59. 5 2

do 150 Triethylene ten-amine 59 1.5 0.5 Methyl epoxy stearate 90 Ethylene rl min 36 gg g. 5 Epoxybutyl stearate 200 1,6 hexylene diamlne 72% triethylene tetramine. 40. 5 go 2 5 2 79 240 175 Epoxidized triacetylated castor oil 175 Diamino propane 27 120 3 Epoxybutyl stearate 150 Cyclo hexyl amine 40. 5 3 Epoxidized soybean oil a. Ethylene dlamine 78% 43 120 3 Epoxidized triacetylated castor oil.. I Cycle hexyl amine 33 115 v 3 Epoxybutyl stearate. 150 Diamino propane. 30. 2 110 3 Epoxidized soybean oil 125 Cyclohexyl amine 46 1%; Epoxidiz'ed triacetylated castor oil "160 Hydro'xyethyl' ethylene'diamlne 35 110-120 3 do Hydra'zine r 12.3 100 3 .Ethomeen 8/15 the reaction. productofifive. moles of ethylene 'oxide and one mole of primary alkyl amine Unadol 40 is an unsaturated C alcohol derived from "Amine" 9 10 and Amine'No. 1 are crudefractions of polyethylene amines. Amine 910 -contains 90% of diethyl- 21 e'ne triamine of triethylene tetramine while amine N0. 1 contains 65% diethylene triamine 25% triethylene tetramine and 10% tctraethylene pentamine.

As previously pointed out, a large proportion of the products described above have one or more basic nitrogen atoms. Thus it is possible to add a high molal acid or low molal acid so as to form a salt with the residual basicity. In a number of instances salt formation changes or alters the solubility of the free base in either oil or water and for a number of purposes makes the salt form more attractive. Where the base has a plurality of basic nitrogen atoms one can neutralize one or more as desired. In general, salt formation with a low molal acid tends to increase water solubility and salt formation with a high molal acid tends to increase oil solubility. Thus, the basic products of reaction can be reacted with low molal acids such as acetic acid, lactic acid, glycolic acid, propionic acid, diglycolic acid and the like. On the other hand one can use naphthenic acid, higher fatty acids, tall oil sulfonic acids, and particularly oil soluble petroleum sulfonic acids such as mahogany acids to form salts.

Table 13 immediately following shows combinations of products which appeared in prior tables combined with various acids illustrating what has been said in this part of the text.

Furthermore, the products described in Part 3 have at least one reactive hydrogen atom on the hydroxyl group formed by rupture of the oxirane ring and hence are susceptible to reaction with an alkylene oxide. Thus to increase their oil solubility they can be treated with one or several moles of, for example, propylene oxide, butylene oxide, styrene oxide, etc.

Sometimes in an effort to maintain a maximum yield of the compound formed by reaction of the materials de scribed in Parts 1 and 2, there may be formed other products as a result of the change which takes place at least'in part after the principal product of reaction has been formed. Without attempting to indicate the variety of complex reactions which can take place and also from the standpoint of indicating why in the hereto attached claims the products are described by method of manufacture, it may be well to illustrate the matter by reference to the cheapest commercially available epoxidized product, to wit, an epoxidized glyceride such as epoxidized soyabean oil.

Such epoxidized glyceride can be reacted with at least 2 moles of a polyamine. Theoretically and actually at least one mole of the polyamine can be caused to react with at least the same number of oxirane rings as appear in the glyceride, i.e., from 2 to 6 moles of the polyamine.

Bearing in mind that the ester can also react to form at least a simple amide, in the same way that soyabean oil, for example, could be reacted with 3 moles of a polyethylene amine to give an amino amide, it is obvious the total number of moles of amine that could be reacted with the glyceride is not only the total number of oxirane 22 rings present in the glyceride but also an additional mole for each acyl radical, i.e., 3 moles more. 1

It is also obvious that one polyamine may unite 2 or more glycerides by supplying a divalent radical. Need less to say, such cross-linking could involvenot only 2 moles of glyceride but 3 or 4 moles.

Since the glyceride, like any other fatty acid equivalent, could act as an acylating agent it is obvious that amides could be formed.

It is well known, of course, that the amides of polyamines which are characterized bya primary amino radical and a secondary amino radical separated by 2 or 3 carbon atoms on heating yield cyclic amidines, and in the case of polyethylene amines yield imidazolines. Various derivatives, of course, also are obtainable, such as amido imidazolines, etc. Without .going further into the compleXity of the invention as herein stated it is obvious it includes a variety of materials resulting from an initial reaction of an oxirane, ring as specified and may result in amidification with the formation of cyclic amidines at a point above the initial reaction temperature and a point below pyrolysis.

PART 4 The compositions herein claimed are merely the result of mechanical mixture. Such mechanical mixture involves only the selection of the particular stabilizer and the addition of a predetermined proportion. Such addition may be made to a conduit or a pipe or a line through which the fuel is flowing, or can be added in a storage tank or in any other suitable container. For the purpose of predetermining an approximate ratio in regard to the stabilizing agent our preference is to use several concern trations of Example A5, 12b or 16b.

:Our preferred test is the comparatively high-temperature short-time test which is noted subsequently in regard to comparative tests with commercially available competitive products. However, a test of the kind described in the first paragraph of column 5 of US. Patent 2,714,051, dated July 26, 1955, to Chenicek, can be employed. Similarly, another suitable test is described in the last paragraph, et seq., of column 4 of US. Patent No. 2,760,852 dated August 28, 1956, to Stevens et al.

In any suitable test our preference is to add to the oil the inhibitor in a range of 15 to 1000 P-PLHL At the end of such test an appropriate ratio can be selected.

Having selected an appropriate ratio, one now can make similar comparative tests with other examples herein described as suitable for stabilization of the fuel. In other words, it simply means the selected test within the appropriate predetermined range would be repeated using one or more examples with the result that some other stabilizer obtained with diiferent reactants could be employed.

Previous reference has been made to comparative tests in which a comparatively high temperature and a comparatively short period of time is employed. Actually, we have examined three commercial products onthe market specifically intended for stabilization as herein described and the tests are reported in the following tables. Note in numerous instances the degree of stability imparted to the fuel by means of one or more of the herein described stabilizing agents is approximately two to three times as good as that of comparative products.

The following are results obtained from a thermal stability test on a commercial diesel fuel having the characteristics set out below:

The test involves heating the oil for minutes at 300 F., cooling for two hours, and filtering through moderately known as a mercaptan gel "in described may be used in conjunction with such other 23 retentive.;fi1ter paper to collectsludge particles. Degradation is determined by observing the degree of stain on the filter paper.

Additive used Ooncentra- Stain tion (p.p.m.)

None Extremely heavy. Commercial 100 'Light. Additive A 11b 50 Moderate. '50 Light.

1 b 50 Moderately heavy.

b i 50 Do.

'50 Moderate.

50 Very light.

' The-following are results obtained froma thermal sta -bility'-t'est=as indicated above but with certain variations.

In this case the heated then cooledoil was filtered through a 'sintered glass filter funnel with a porosity designed to reta'in' particles of 414.01 larger. The sludge particles were then "dissolved inanacetone-methanol mixture, the

solution was drawn otfintoa tared beaker, and the solvent was removed by evaporation. Degradation products'were then determined gravimetrically on an analytical balance. An additional test, in which color degradation was measured, was applied. The instrument for measuring color was .the AC Model Fisher Electrophotomer using Filter No. 510-A and n-Heptane set at zero O.D.U. Sludge is reported in nag/100 ml. and color in optical density units.

Under certain circumstances it is desirable to add a stabilizer to fuel which functions to prevent or affect some other'property rather than sludge formation or discoloration .as herein described. For instance, a metal deactivatormaybe added which prevents the formation of gums,'which maybe for the present purpose differentiated from sludges. Such metal deactivators prevent what is or body. The stabilizers herestabilizers.

We claim: '1."As a 'fuel'oil having a boiling'rangeof 135 F. to 700 F. composition, a distilled hydrocarbon fuel contain- .ing a small amount suificient to stabilize the fuel with respect to the formation of sludge and undesirable color bodies of the products obtained by reacting at a temperaftureof about 100 to 300 C. for from about 1 to 4 24 hours (A) an oxirane ring containing compound selected from the-class. consisting of epoxidized higher fatty acids, epoxidized lower alkanol esters of higher fatty acids, epoxidized amides of lower alkyl amines and fatty acids, epoxidized higher fatty alcohols and epoxidized'higher fatty acids glycerides, with (B) an oxyalkylatiomsusceptible nitrogen containing compound selected from'the class consisting of hydrazine and monoamino and polyamino compounds composed of carbon, hydrogemoxygen and nitrogen atoms, having only functional groupsselected from the class consisting of hydroxyl groups, primary amino groups and secondary aminorgroups and havin g at .least one such functional amino group; said reaction between (A) and (B) involving rupture of each oxirane ring and resulting in the formation of at least one of the following groupings 2. The fuel composition of claim 1 wherein the oxirane ring containing compound is epoxidized triacetylatedcastor oil.

3. The fuel composition of claim 1 wherein the oxirane ring containing compound is epoxybutyl stearate.

4. The fuel composition of claim 1 wherein the oxirane ring containing compound is epoxidized soyabeano'il.

5. The fuel composition of claim 1 wherein the oxirane ring containing compound is epoxidized triacetylated cas- -t0r oil and the oXyalkylation-susceptible nitrogen. contain- "ring containing compound is epoxybutyl stearate and the oXyalkylation-susceptible nitrogen containing compound is diamino propane.

9. The fuel composition of claim 1 wherein the oxirane ring containing compound is epoxidized soyabean oil and the oxyalkylation-susceptible nitrogen containing compound is cyclohexylamine.

References Cited in the file of this patent UNITED STATES PATENTS 2,445,892 Swern et a1 July 27, 1948 2,840,600 Du Brow et al. June 24, 1958 2,851,344 Marsh et a1. Sept. 9, 1958 2,851,345 Marsh et a1 Sept. 9, 1958 

1. AS A FUEL OIL HAVING A BOILING RANGE OF 135* F. TO 700* F. COMPOSITION, A DISTILLED HYDROCARBON FUEL CONTAINING A SMALL AMOUNT SUFFICIENT TO STABILIZE THE FUEL WITH RESPECT TO THE FORMATION OF SLUDGE AND UNDESIRABLE COLOR BODIES OF THE PRODUCTS OBTAINED BY REACTING AT A TEMPERATURE OF ABOUT 100* TO 300* C. FOR FROM ABOUT 1 TO 4 HOURS (A) AN OXIRANE RING CONTAINING COMPOUND SELECTED FROM THE CLASS CONSISTING OF EPOXIDIZED HIGHER FATTY ACIDS, EPOXIDIZED LOWER ALKANOL ESTERS OF HIGHER FATTY ACIDS, EPOXIDIZED AMIDES OF LOWER ALKYL AMINES AND FATTY ACIDS, EPOXIDIZED HIGHER FATTY ALCOHOLS AND EPOXIDIZED HIGHER FATTY ACIDS GLYCERIDES, WITH (B) AN OXYALKYLATION-SUSCEPTIBLE NITROGEN CONTAINING COMPOUND SELECTED FROM THE CLASS CONSISTING OF HYDRAZINE AND MONOAMINO AND POLYAMINO COMPOUNDS COMPOSED OF CARBON, HYDROGEN, OXYGEN AND NITROGEN ATOMS, HAVING ONLY FUNCTIONAL GROUPS, PRIMARY FROM THE CLASS CONSISTING OF HYDROXYL GROUPS, PRIMARY AMINO GROUPS AND SECONDARY AMINO GROUPS AND HAVING AT LEAST ONE SUCH FUNCTIONAL AMINO GROUP; SAID REACTION BETWEEN (A) AND (B) INVOLVING RUPTURE OF EACH OXIRANE RING AND RESULTING IN THE FORMATION OF AT LEAST ONE OF THE FOLLOWING GROUPINGS. 